CN102311455A - Radiation-curable polyfunctional (meth)acrylic ester combination containing phosphonic group and preparation method thereof - Google Patents
Radiation-curable polyfunctional (meth)acrylic ester combination containing phosphonic group and preparation method thereof Download PDFInfo
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- CN102311455A CN102311455A CN201110129751A CN201110129751A CN102311455A CN 102311455 A CN102311455 A CN 102311455A CN 201110129751 A CN201110129751 A CN 201110129751A CN 201110129751 A CN201110129751 A CN 201110129751A CN 102311455 A CN102311455 A CN 102311455A
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- Prior art keywords
- acid
- phosphonate group
- methyl
- reaction
- polyvalent alcohol
- Prior art date
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- -1 acrylic ester Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000000047 product Substances 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 230000032050 esterification Effects 0.000 claims description 20
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 13
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 11
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007046 ethoxylation reaction Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical group C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007039 two-step reaction Methods 0.000 claims description 3
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 claims description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 claims description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- ZCHGODLGROULLT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;propane-1,2-diol Chemical compound CC(O)CO.OCC(CO)(CO)CO ZCHGODLGROULLT-UHFFFAOYSA-N 0.000 claims description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004258 Ethoxyquin Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 241000545067 Venus Species 0.000 claims description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 claims description 2
- MUAXETKHGSOSCB-UHFFFAOYSA-N copper;2-methylprop-2-enoic acid Chemical compound [Cu].CC(=C)C(O)=O MUAXETKHGSOSCB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229940061607 dibasic sodium phosphate Drugs 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093500 ethoxyquin Drugs 0.000 claims description 2
- 235000019285 ethoxyquin Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- JNQXVIAROPTRDY-UHFFFAOYSA-N manganese;2-methylprop-2-enoic acid Chemical compound [Mn].CC(=C)C(O)=O JNQXVIAROPTRDY-UHFFFAOYSA-N 0.000 claims description 2
- DMZUKDRIRUYBIU-UHFFFAOYSA-N manganese;prop-2-enoic acid Chemical compound [Mn].OC(=O)C=C DMZUKDRIRUYBIU-UHFFFAOYSA-N 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000003847 radiation curing Methods 0.000 abstract description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- GUXRZQZCNOHHDO-UHFFFAOYSA-N 2-phosphonopropanoic acid Chemical compound OC(=O)C(C)P(O)(O)=O GUXRZQZCNOHHDO-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- APZPSKFMSWZPKL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)CO APZPSKFMSWZPKL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Abstract
The invention relates to a polyfunctional (meth)acrylic ester combination containing phosphonic group and the combination is prepared by virtue of two steps of reactions. The combination is prepared by the following method: (1) reacting a polyhydric alcohol with acrylic acid or methacrylic acid, and controlling material ratio to control that the reaction product contains an esterified product with the whole hydroxyl group esterified and an esterified product with one hydroxyl group unesterified; and (2) reacting the esterified product with one hydroxyl group unesterified with an organic carboxylic acid containing phosphonic group to obtain the polyfunctional (meth)acrylic ester combination containing phosphonic group. The obtained combination can be applied to a radiation curing reaction system. Compared with the existing polyfunctional methacrylic ester containing phosphonic group, the prepared polyfunctional (meth)acrylic ester combination containing phosphonic group has better hydrolytic stability when used as an adhesion accelerator of base materials such as metal and the like in the radiation curing system.
Description
Technical field
The present invention relates to the composition and method of making the same of multifunctional (methyl) propenoate that contains phosphonate group in compound synthetic field, particularly a kind of radiation-hardenable, can be applicable to the radiation curing reaction system and as the adhesion promoter of metal base.
Background technology
(methyl) propenoate can solidify through radiation (uviolizing or electron beam irradiation), and the blending composition that can be used as the radiation curing constituent is used in the various industrial uses of coating, tackiness agent, printing seal China ink (like PCB printing ink) etc.In radiation curable coating, tackiness agent, the printing seal China ink, often need to add multifunctional (methyl) propenoate improving its reactivity, or give the high cross-linking density of cured prod etc.For metal base, need add (methyl) propenoate that contains (phosphine) phosphate especially or contain (phosphine) phosphoric acid functionalized multifunctional (methyl) propenoate as adhesion promoter.
Its commercially produced product of polyvalent alcohol (methyl) propenoate often has the form of mixture; Contain pentaerythritol triacrylate simultaneously like tetramethylol methane tetraacrylate; Double pentaerythritol methacrylate contains double pentaerythritol C5 methacrylate simultaneously, both not thoroughly reactions of polyvalent alcohol.
The method of alkyd direct esterification is generally all adopted in the preparation of polyvalent alcohol (methyl) propenoate, and polyvalent alcohol and (methyl) vinylformic acid in the presence of catalyzer, stopper and solvent, are reacted under the solvent refluxing condition.In reaction process, will react the water that generates through solvent and water azeotropic and constantly take out of outside the reaction system, reaction is carried out to the esterification direction.Polyvalent alcohol (methyl) propenoate of this method preparation, its functional group's number receives the restriction of polyvalent alcohol hydroxyl value.Receive the restriction of the contained hydroxyl value of polyvalent alcohol; (methyl) propenoate of high functionality more; Be to prepare polyester polyol with polyvalent alcohol earlier, form with (methyl) acroleic acid esterification again, but the general polyvalent alcohol of the price of dimethylol propionic acid or dimethylolpropionic acid is high by dimethylol propionic acid or dimethylolpropionic acid; (methyl) propenoate cost of the polyfunctionality that makes like this is higher, has restricted its application to a certain extent.
(methyl) propenoate that contains (phosphine) phosphate adds the radiation curing system, can better increase its sticking power for metal base, solder resist etc.In the disclosed file of Chinese patent CN1077470A, with pentaerythritol triacrylate and Vanadium Pentoxide in FLAKES reaction, prepared the propenoate of the trifunctional of phosphorous acidic group, be applied to photosensitive solder resist and make adhesion promoter.In disclosed japanese patent laid-open 3-294286 communique file; The organic carboxyl acid that contains phosphonate group and hydroxyethyl methacrylate second (third, fourth etc.) ester reaction has been discussed; The esterification of carboxylic acid group and hydroxyl rather than the esterification of phosphonate group and hydroxyl take place selectively, and the prepared methacrylic ester that contains phosphonate group is applied to tooth section tackiness agent.In disclosed US6172131 document us, phosphonic acids that contains acryl or phosphonic acid ester (it is strong the to contain P-C) compound described as tooth section tackiness agent have stability to hydrolysis preferably than phosphonic acids that contains acryl or phosphonic acid ester (it is strong not contain P-C) compound.
Summary of the invention
One of the object of the invention is the above-mentioned deficiency that overcomes prior art, and the compsn of multifunctional (methyl) propenoate that contains phosphonate group of a kind of radiation-hardenable is provided.
Technical scheme of the present invention is: the compsn of multifunctional (methyl) propenoate that contains phosphonate group of a kind of radiation-hardenable, and it prepares through following method:
The first step is a starting raw material with polyvalent alcohol, (methyl) vinylformic acid, adds solvent, stopper, catalyzer, under refluxad carries out esterification; Utilize solvent that the water band that esterification produces is left reaction system; After the generation water yield reaches requirement, be cooled to solvent and do not reflux, termination reaction;
Second step was in the reaction mixture of the first step, added the organic carboxyl acid that contains phosphonate group, proceeded esterification; After the generation water yield reaches requirement; Be chilled to room temperature,, add MEHQ through washing; Remove solvent under the decompression state, promptly get the compsn of multifunctional (methyl) propenoate that contains phosphonate group after the filtration.
Pass through the control material ratio during the first step reaction; Make initial polyvalent alcohol and acrylic or methacrylic acid-respons with m hydroxyl; If the polyvalent alcohol add-on is 1 mol, the add-on of then controlling acrylic or methacrylic acid, makes in the reaction product and contains greater than (m-1) mol and permanent in m mol for permanent: only have in the polyvalent alcohol molecule that is added 1 hydroxyl not with the product B of acrylic or methacrylic acid estersization; And contain in the polyvalent alcohol molecule all product A of hydroxyls and acrylic or methacrylic acid estersization; The content perseverance of product A is greater than 0, preferred 5-50%, preferred especially 5-20%;
Second step reaction: let the product B of the first step reaction and the organic carboxyl acid that contains phosphonate group react; Make B excessive; To guarantee that the organic carboxyl acid that contains phosphonate group reacts completely, promptly end product contain product B in the compsn of multifunctional (methyl) propenoate of phosphonate group the content perseverance greater than 0.
Described polyvalent alcohol can be terepthaloyl moietie, NSC 6366,1; Ammediol, 1; 6-pinakon, 2-ethyl-1; Ammediol, 2-methyl isophthalic acid; Ammediol, glycol ether, Tri Ethyleneglycol, ethoxylation NSC 6366, ethoxylated neopentylglycol, ethoxylation-1; 6-pinakon, polyoxyethylene glycol, DPG, tripropylene glycol, l, 4-butyleneglycol, ethoxylation dihydroxyphenyl propane, 1,4 cyclohexane dimethanol, 1; 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, three light methylpropanes, ditrimethylolpropane, ethoxylated trimethylolpropane, propoxylation TriMethylolPropane(TMP), glycerine, ethoxyquin glycerine, glycerol propoxylate, trishydroxymethyl tricarbimide, three (2-hydroxyethyl) tricarbimide, three (hydroxypropyl) tricarbimide, tetramethylolmethane, ethoxylation tetramethylolmethane, pentaerythritol propoxylate, NSC 65881.
The described organic carboxyl acid that contains phosphonate group has phosphonate group and carboxylic acid group simultaneously in its molecule, structure is following:
Wherein: n=n1+n2+n3, the value of n1, n2, n3 all can be: 0,1,2,3, the value of n1, n2, n3 can not be 0 simultaneously, but one of them or two are 0, n≤3; X=H, OH;
R
1, R
2, R
3Be C
0-12Straight chain or branch's alkylidene group, C
3-8Cyclic alkylidene, phenylene, biphenylene, naphthylidene, xylylene ,-the Ph-A-Ph-base, wherein A is (CH
2)
m(m=1～6) ,-O-or-S-;
R
1, R
2, R
3Can be identical, or inequality, or wherein two identical;
R
1, R
2, R
3Base can have one or more hydroxyls (OH).
The described organic carboxyl acid that contains phosphonate group can be phosphine acyl acetic acid (n
2=n
3=0, X=H, R
1=no substituted alkylene), phosphono propionic acid (n
2=n
3=0, X=H, R
1=CH
2), 2-HPAA (n
2=n
3=0, X=OH, R
1=no substituted alkylene), 2-phosphonic acids butane-1,2,4-tricarboxylic acid (n
1=n
2=n
3=1, X=H, R
1=no substituted alkylene, R
1=CH
2, R
1=C
2H
4).
Described solvent can be toluene, benzene, hexanaphthene, methylcyclohexane, normal heptane, Iso Butyl Acetate, isobutyl acetate, 2-butyl acetate.
Described stopper can be thiodiphenylamine, Resorcinol, to through basic methyl-phenoxide, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2; 4-xylenol, 2; 6-di-tert-butyl-4-methy phenol, 2-tert.-butyl phenol, 4-tert.-butyl phenol, 2; 4-DI-tert-butylphenol compounds, 2-first-4-tert.-butyl phenol, the 4-tertiary butyl-2, one or more combinations in 6-xylenol, Hypophosporous Acid, 50, phosphorous acid, venus crystals, cupric chloride, copper sulfate, vinylformic acid ketone, methylacrylic acid copper, manganous acetate, Manganous chloride tetrahydrate, manganous sulfate, vinylformic acid manganese, methylacrylic acid manganese, oil of mirbane, the PNT.
Described catalyzer can be one or more mixtures in the following compound: sulfuric acid, methanesulfonic, 2-naphthene sulfonic acid, a benzene disulfonic acid, tosic acid, trifluoromethanesulfonic acid, monoammonium sulfate, sodium pyrosulfate, sal enixum, tetramethyl-monoammonium sulfate, Sodium phosphate, dibasic, potassium hydrogenphosphate, Secondary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate.
Said each item add-on is according to following weight percent: solvent is polyvalent alcohol, (methyl) vinylformic acid, contain phosphonate group the organic carboxyl acid total amount 5～60%, preferred 15～35%; Catalyzer is polyvalent alcohol, (methyl) vinylformic acid, contain phosphonate group the organic carboxyl acid total amount 1～5%, preferred 1. 5～3. 5%; Stopper be polyvalent alcohol, (methyl) vinylformic acid, phosphonate group the organic carboxyl acid total amount 0. 1～2. 5%, preferred 0. 5～1. 5%.
In the said two-step reaction, the temperature of esterification is 60～140 ℃, preferred 80～120 ℃.
The reaction formula (being combined as example with tetramethylolmethane, vinylformic acid, 2-HPAA) of multifunctional (methyl) propenoate that contains phosphonate group of the present invention is as follows:
The first step reaction:
The reaction of second step:
Total overall reaction is chilled to room temperature with reaction mixture after finishing, and washes, adds MEHQ afterwards, and vacuum desolventizes, filters, and gets the compsn of multifunctional (methyl) propenoate that contains phosphonate group of radiation-hardenable of the present invention.
Two of the object of the invention is the above-mentioned deficiencies that overcome prior art, and the preparation of compositions method of multifunctional (methyl) propenoate that contains phosphonate group of a kind of radiation-hardenable is provided.
Technical scheme of the present invention is: the preparation of compositions method of multifunctional (methyl) propenoate that contains phosphonate group of a kind of radiation-hardenable comprises following process step:
The first step is a starting raw material with polyvalent alcohol, (methyl) vinylformic acid, adds solvent, stopper, catalyzer, under refluxad carries out esterification; Utilize solvent that the water band that esterification produces is left reaction system; After the generation water yield reaches requirement, be cooled to solvent and do not reflux, termination reaction;
Second step was in the reaction mixture of the first step, added the organic carboxyl acid that contains phosphonate group, proceeded esterification; After the generation water yield reaches requirement; Be chilled to room temperature,, add MEHQ through washing; Remove solvent under the decompression state, promptly get the compsn of multifunctional (methyl) propenoate that contains phosphonate group after the filtration.
Pass through the control material ratio during the first step reaction; Make initial polyvalent alcohol and acrylic or methacrylic acid-respons with m hydroxyl; If the polyvalent alcohol add-on is 1 mol, the add-on of then controlling acrylic or methacrylic acid, makes in the reaction product and contains greater than (m-1) mol and permanent in m mol for permanent: only have in the polyvalent alcohol molecule that is added 1 hydroxyl not with the product B of acrylic or methacrylic acid estersization; And contain in the polyvalent alcohol molecule all product A of hydroxyls and acrylic or methacrylic acid estersization; The content perseverance of product A is greater than 0, preferred 5-50%, preferred especially 5-20%;
The reaction of second step lets the product B of the first step reaction and the organic carboxyl acid that contains phosphonate group react; Make B excessive; To guarantee that the organic carboxyl acid that contains phosphonate group reacts completely, promptly end product contain product B in the compsn of multifunctional (methyl) propenoate of phosphonate group the content perseverance greater than 0.
It is reversible reaction that the present invention makes full use of esterification; And be these two characteristics of progressively carrying out; Utilize polyvalent alcohol and acrylic or methacrylic acid-respons (hydroxyl groups is total overall reaction not) earlier; React with the organic carboxyl acid that contains phosphonate group more afterwards; Both adopt two-step reaction preparation to contain multifunctional (methyl) propenoate of phosphonate group, through different polyvalent alcohols, contain the combination of the organic carboxyl acid of phosphonate group, obtained multifunctional (methyl) propenoate that series contains phosphonate group; Can be at the adhesion promoter of radiation curing system as base materials such as metals, have better stability to hydrolysis than the methacrylic ester of existing phosphorous acidic group and also have high functionality.
Below in conjunction with embodiment detailed content of the present invention is further described.
Embodiment
Embodiment 1: preparation contains the compsn of the trifunctional propenoate of phosphonate group
In 1000 ml four-hole reaction flasks; Distribution moves stirring, TM, water trap, condensing surface; Add 230 g tetramethylolmethanes, 390 g vinylformic acid, 160 g toluene, 22.8 g tosic acid, 7.6 g MEHQs, 3.8 g thiodiphenylamine successively, heat temperature raising to system is reflux state, and toluene and water azeotropic will react the water that generates and take out of outside the system through water trap; Moisture goes out and reacting liquid temperature stable until no longer including; Can be considered the first step reaction end, reaction mixture is cooled to solvent does not reflux, termination reaction; The reaction of second step: in reaction solution, add 185 g 2-phosphine acyl acetic acids, heating up again makes system keep reflux state, and the water of generation and methylbenzene azeotropic are taken system out of through water trap; Moisture goes out and reacting liquid temperature stable until no longer including, and is regarded as the second step reaction end, and reaction mixture is chilled to room temperature; Through washing; Add 0.240 g MEHQ, remove toluene under the decompression state, the outlet temperature that removes the toluene process is 5 ℃ of 90 scholars; Vacuum tightness is 20～30 mmHg, through filtering the acrylate composition of the trifunctional propenoate that contains phosphonate group.
Embodiment 2: preparation contains the compsn of the trifunctional methacrylic ester of phosphonate group
In 1000 ml four-hole reaction flasks; Distribution moves stirring, TM, water trap, condensing surface, adds 220 g 1 successively, 6-pinakon, 255 g methylacrylic acids, 150 g hexanaphthenes, 20.8 g methanesulfonics, 7.5 g MEHQs, 3.3 g Resorcinol; Heat temperature raising to system is reflux state; Hexanaphthene and water azeotropic will react the water that generates to be taken out of outside the system through water trap, and moisture goes out and reacting liquid temperature stable until no longer including, and can be considered the first step reaction end; Reaction mixture is cooled to solvent does not reflux, termination reaction; Second step reaction: in reaction solution, add 221 g 2-phosphonic acids butane-1,2,4-tricarboxylic acid; Again heating up makes system keep reflux state, and the water of generation and hexanaphthene azeotropic are taken system out of through water trap, and moisture goes out and reacting liquid temperature stable until no longer including; Be regarded as the second step reaction end, reaction mixture is chilled to room temperature, through washing; Add 0.300 g MEHQ, remove hexanaphthene under the decompression state, the outlet temperature that removes the hexanaphthene process is 5 ℃ of 70 scholars; Vacuum tightness is 20～30 mmHg, through filtering the methacrylate compositions of the trifunctional methacrylic ester that contains phosphonate group.
Embodiment 3: preparation contains the compsn of the face ability propenoate of phosphonate group
In 1000 ml four-hole reaction flasks; Distribution moves stirring, TM, water trap, condensing surface; Add 220 g NSC 65881s, 350 g vinylformic acid, 220 g methylcyclohexanes, the 10.2 g vitriol oils, 3.2 g copper sulfate, 3.1 g MEHQs successively, heat temperature raising to system is reflux state, and methylcyclohexane and water azeotropic will react the water that generates and take out of outside the system through water trap; Moisture goes out and reacting liquid temperature stable until no longer including; Can be considered the first step reaction end, reaction mixture is cooled to solvent does not reflux, termination reaction; The reaction of second step: in reaction solution, add 116 g 2-HPAAs, heating up again makes system keep reflux state, and the water of generation and methylcyclohexane azeotropic are taken system out of through water trap; Moisture goes out and reacting liquid temperature stable until no longer including, and is regarded as the second step reaction end, and reaction mixture is chilled to room temperature; Through washing; Add 0.280 g MEHQ, remove methylcyclohexane under the decompression state, the outlet temperature that removes the methylcyclohexane process is 5 ℃ of 80 scholars; Vacuum tightness is 20～30 mmHg, through filtering the acrylate composition of the face ability propenoate that contains phosphonate group.
Embodiment 4: preparation contains the compsn of six sense methacrylic esters of phosphonate group
In 1000 ml four-hole reaction flasks; Distribution moves stirring, TM, water trap, condensing surface; Add 222 g TriMethylolPropane(TMP)s, 320 g methylacrylic acids, 70 g normal heptanes, 13.8 g monoammonium sulfates, 7.8 g manganous acetates, 3.8 g MEHQs successively, heat temperature raising to system is reflux state, and normal heptane and water azeotropic will react the water that generates and take out of outside the system through water trap; Moisture goes out and reacting liquid temperature stable until no longer including; Be regarded as the first step reaction end, reaction mixture be cooled to solvent do not reflux, termination reaction; Second step reaction: in reaction solution, add 142g 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid; Again heating up makes system keep reflux state, and the water of generation and normal heptane azeotropic are taken system out of through water trap, and moisture goes out and reacting liquid temperature stable until no longer including; Be regarded as the second step reaction end, reaction mixture is chilled to room temperature, through washing; Add 0.280 g MEHQ, remove normal heptane under the decompression state, the outlet temperature that removes the normal heptane process is 5 ℃ of 70 scholars; Vacuum tightness is 20～30 mmHg, through filtering the methacrylate compositions of the six sense methacrylic esters that contain phosphonate group.
Claims (10)
1. the compsn of multifunctional (methyl) propenoate that contains phosphonate group of a radiation-hardenable; It is characterized in that through the preparation of following method: the first step is a starting raw material with polyvalent alcohol, (methyl) vinylformic acid, adds solvent, stopper, catalyzer, under refluxad carries out esterification; Utilize solvent that the water band that esterification produces is left reaction system; After the generation water yield reaches requirement, be cooled to solvent and do not reflux, termination reaction; Second step was in the reaction mixture of the first step, added the organic carboxyl acid that contains phosphonate group, proceeded esterification; After the generation water yield reaches requirement; Be chilled to room temperature,, add MEHQ through washing; Remove solvent under the decompression state, promptly get the compsn of multifunctional (methyl) propenoate that contains phosphonate group after the filtration; Pass through the control material ratio during the first step reaction; Make initial polyvalent alcohol and acrylic or methacrylic acid-respons with m hydroxyl; If the polyvalent alcohol add-on is 1 mol, the add-on of then controlling acrylic or methacrylic acid, makes in the reaction product and contains greater than (m-1) mol and permanent in m mol for permanent: only have in the polyvalent alcohol molecule that is added 1 hydroxyl not with the product B of acrylic or methacrylic acid estersization; And contain in the polyvalent alcohol molecule all product A of hydroxyls and acrylic or methacrylic acid estersization; The content perseverance of product A is greater than 0, preferred 5-50%, preferred especially 5-20%; Second step reaction: let the product B of the first step reaction and the organic carboxyl acid that contains phosphonate group react; Make B excessive; To guarantee that the organic carboxyl acid that contains phosphonate group reacts completely, promptly end product contain product B in the compsn of multifunctional (methyl) propenoate of phosphonate group the content perseverance greater than 0.
2. compsn according to claim 1; It is characterized in that described polyvalent alcohol can be terepthaloyl moietie, NSC 6366,1; Ammediol, 1; 6-pinakon, 2-ethyl-1; Ammediol, 2-methyl isophthalic acid, ammediol, glycol ether, Tri Ethyleneglycol, ethoxylation NSC 6366, ethoxylated neopentylglycol, ethoxylation-1,6-pinakon, polyoxyethylene glycol, DPG, tripropylene glycol, l; 4-butyleneglycol, ethoxylation dihydroxyphenyl propane, 1; 4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, three light methylpropanes, ditrimethylolpropane, ethoxylated trimethylolpropane, propoxylation TriMethylolPropane(TMP), glycerine, ethoxyquin glycerine, glycerol propoxylate, trishydroxymethyl tricarbimide, three (2-hydroxyethyl) tricarbimide, three (hydroxypropyl) tricarbimide, tetramethylolmethane, ethoxylation tetramethylolmethane, pentaerythritol propoxylate, NSC 65881.
3. described compsn according to claim 1 is characterized in that solvent can be toluene, benzene, hexanaphthene, methylcyclohexane, normal heptane, Iso Butyl Acetate, isobutyl acetate, 2-butyl acetate.
4. described compsn according to claim 1; It is characterized in that described stopper can be thiodiphenylamine, Resorcinol, to through basic methyl-phenoxide, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2; 4-xylenol, 2; 6-di-tert-butyl-4-methy phenol, 2-tert.-butyl phenol, 4-tert.-butyl phenol, 2; 4-DI-tert-butylphenol compounds, 2-first-4-tert.-butyl phenol, the 4-tertiary butyl-2, one or more combinations in 6-xylenol, Hypophosporous Acid, 50, phosphorous acid, venus crystals, cupric chloride, copper sulfate, vinylformic acid ketone, methylacrylic acid copper, manganous acetate, Manganous chloride tetrahydrate, manganous sulfate, vinylformic acid manganese, methylacrylic acid manganese, oil of mirbane, the PNT.
5. described compsn according to claim 1 is characterized in that described catalyzer can be one or more mixtures in the following compound: sulfuric acid, methanesulfonic, 2-naphthene sulfonic acid, a benzene disulfonic acid, tosic acid, trifluoromethanesulfonic acid, monoammonium sulfate, sodium pyrosulfate, sal enixum, tetramethyl-monoammonium sulfate, Sodium phosphate, dibasic, potassium hydrogenphosphate, Secondary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate.
6. the compsn described according to claim 1-5 is characterized in that said each item add-on is according to following weight percent: solvent is polyvalent alcohol, (methyl) vinylformic acid, contain phosphonate group the organic carboxyl acid total amount 5～60%, preferred 15～35%; Catalyzer is polyvalent alcohol, (methyl) vinylformic acid, contain phosphonate group the organic carboxyl acid total amount 1～5%, preferred 1. 5～3. 5%; Stopper be polyvalent alcohol, (methyl) vinylformic acid, phosphonate group the organic carboxyl acid total amount 0. 1～2. 5%, preferred 0. 5～1. 5%.
7. described compsn according to claim 1 is characterized in that in the said two-step reaction that the temperature of esterification is 60～140 ℃, preferred 80～120 ℃.
8. described compsn according to claim 1, it is characterized in that containing phosphonate group multifunctional (methyl) propenoate reaction formula (being combined as example) with tetramethylolmethane, vinylformic acid, 2-HPAA as follows:
The first step reaction:
The reaction of second step:
Total overall reaction is chilled to room temperature with reaction mixture after finishing, and washes, adds MEHQ afterwards, and vacuum desolventizes, filters, and gets the compsn of multifunctional (methyl) propenoate that contains phosphonate group of radiation-hardenable of the present invention.
9. the preparation of compositions method of multifunctional (methyl) propenoate that contains phosphonate group of a radiation-hardenable; It is characterized in that the first step is a starting raw material with polyvalent alcohol, (methyl) vinylformic acid, add solvent, stopper, catalyzer, under refluxad carry out esterification; Utilize solvent that the water band that esterification produces is left reaction system; After the generation water yield reaches requirement, be cooled to solvent and do not reflux, termination reaction; Second step was in the reaction mixture of the first step, added the organic carboxyl acid that contains phosphonate group, proceeded esterification; After the generation water yield reaches requirement; Be chilled to room temperature,, add MEHQ through washing; Remove solvent under the decompression state, promptly get the compsn of multifunctional (methyl) propenoate that contains phosphonate group after the filtration.
10. described preparation of compositions method according to claim 9; Pass through the control material ratio when it is characterized in that the first step reaction; Make initial polyvalent alcohol and acrylic or methacrylic acid-respons with m hydroxyl; If the polyvalent alcohol add-on is 1 mol, the add-on of then controlling acrylic or methacrylic acid, makes in the reaction product and contains greater than (m-1) mol and permanent in m mol for permanent: only have in the polyvalent alcohol molecule that is added 1 hydroxyl not with the product B of acrylic or methacrylic acid estersization; And contain in the polyvalent alcohol molecule all product A of hydroxyls and acrylic or methacrylic acid estersization; The content perseverance of product A is greater than 0, preferred 5-50%, preferred especially 5-20%; Second step reaction: let the product B of the first step reaction and the organic carboxyl acid that contains phosphonate group react; Make B excessive; To guarantee that the organic carboxyl acid that contains phosphonate group reacts completely, promptly end product contain product B in the compsn of multifunctional (methyl) propenoate of phosphonate group the content perseverance greater than 0.
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Application publication date: 20120111 |